Halogenated dye and process of making same.



' containing a bei'izanthrone grouping :-treatment with-alkali, and which are llLIllll- .UNrTEn- -sm'rns .IPATENT torsion;

OSCAR BALLYJOF MANNHEIM, GI'IRMANY..-ASSIGNOR T BADISCHE ANILIN & SODA FABRIK, OF LUDWiGSHAFEN-ON-THE-RHINE,

GERMANY, A CORPORATION.

HALOGENATED DYE AND PROCESS OF MAKlNG SAME- Specification of Letters Patent,

.Patented .Dec. 4, 1906.

of philosophy and chemist, a ('ltlZPlLOf the:

Sw1ss Republic, residing at Mannheim, in the Grand..-Duc-hy of Baden, German Empire, have invented new and useful Improvements in Halogenated Dyes and Processes of 1 ing Same, of which the following is-a specification.

I have discovered that coloring-matters such as can be obtained from compounlds n after termed benzanthrone coloring-matters, (see, for example, the specifications of Letters Patent .Nos. 809,892, 811,471, and

818,336 and of the applications for Letters Nos. 282,187 and 282,356,)

trating agent, (see, for example, the specification of Letters Patent No, 796,393,) can by treatment with a halogenizing agentsuch. for instance, as halogen itself or sulfuroxychlorid-be converted into their halogen derivatives.

The new coloring-mattersobtained in ac cordance -swith the present invention diller l fi'o1n the originalcoloring-matters both in shade and in their chemical reactions, being generally more easily converted into their euco compounds in the vat. My new coloringmatters are claimed enerically in Letters Patent N 0. 818,336, which claims the produc '-tion of coloring-matters from a halogenated benzanthrone, and they possess the same genthe coloring-matters I eral characteristics as claimed in the said specificationthat is to say, the are, when dry, powders ranging from dar violet to brown-violet, and are insoluble in Water and in alcohol and are soluble in alkaline hydrosulfite. They are, however, su erior to these latter in being more easily so uble in the vat, and therefore better suited for printing onto textile fiber and also in yielding clearer, shades of violet. They are soluble in hot anilin,yielding from green to blue-violet solutions.

The following examples will serve to further illustrate the nature of my invention and the manner in which it can be carried into practical effect but my invention is not confined to these examples. The parts are by weight:

a current of dry Example I: Suspend one (1) art of-cyamanthrene (the coloring-matter o tainable ae- 555 wording to Example 1 of the specification of Letters Patent No. 809,892) in ten (10) parts of glacial acetic acid, add four (4) parts of broniiu, and boil the whole in a reflux apparatus until the evolution of hydrobromic acid ceases. Allow the mass to cool, filter oil the -color-i1ig-nmtter, wash it with glacial acetic acid, and dry it. The bromcyananthrene so obtained dissolves in concentrated --sulfuric acid, yielding a dull-green solution. In hot '5 nit robenzeneit is dillicultly soluble, yielding a greenish solution with a browrrred' fluorescence. It is soluble in hot anilin,yieldin a blue-green solution,.and it dissolves in al aline hydrosulfite, yielding a blue solution which dyes cotton violet-blue shades.

Example 2: Suspend one (1) part of cyananthrene in ten (10) parts of nitrobenzene, and while at ordinary temperature add one (1) part of sulfuroxychlorid and then heat the mixture at a temperature of from sixt (60) to seventy (70) degrees centigrade unt1l the evolution of hydrochloric acid'ceases. Then precipitate by means of alcohol the chlorcyananthrene, filter it, wash it with al-- echo], and dry it. This coloring-matter differs from that produced according to the foregoing Example 1 in that its so ution in concentrated sulfuric acid is pure green and that its solution in hot anilin is greenish-blue. It dyes cotton blue-violet shades. 1

Example 3: Suspend one (1) part of cyananthene in ten (10) parts of nitrobenzene and while at a temperature of from sixty (60) to seventy (70) degrees centigrade pass 0 chlorin through the suspension until a test portion ofthe product after being precipitated by means of alcohol yields a greenish-blue solution in alkaline hydrosuliite. Then isolate the coloring-matter in 5 the manner described in the fore oing Example 2. The coloring-matter yie ds a bluegreen solution in concentrated sulfuric acid, and it is more easily soluble in nitrobenzene than are the coloring-matters prepared ac 10o cording to the foregoing examples, and in this solvent its solution is blue wlth a brownred fluorescence. Its solution in hot anilin is blue and in alkaline hydrosulfite greenish- Jalue, and it dyes cotton a warm violet.

This invention is not limited to the use of 2o blue-violet.

nitrobenzene and of glacial acetic acid, as other indifierent suspension agents or solvents can be used, and instead of sulfur oxychlorid or chlorin or bromin other halogen- 5 izing agents may be used.

Instead of cyananthrene other coloring matters, such as can be produced in the manner above mentioned from benzanthrones or from benzanthronequinolins can be employed.

:0 For instance, violanthrene (the coloring-mat ter obtainable according to the example of the specification of the application for Letters Patent Serial No. 282,217) when treated according to the methods iven in the foregoing examples yields ha ogenated coloringmatters which dissolve in hot nitrobenzene, the solutions being from violet to violet-blue and having a brown-red fluorescence, the solu tions in hot anilin being from green-blue to In alkaline hydrosulfite they yield from violet-red to green-blue vats which dye cotton shades varying from violet blue to red-violet.

Now what I claim isr 1. The process for the production of coloring-matters containing halogen by treatin a benzanthrone coloring-matter with a ha 0- genizing agent.

2. The process for the production of color- 30 ing-matter conta ning halogen by treating cyananthrene with a halogenizing agent.

3Q The process for the production of coloring inatter containin halogen by treating cyananthrene with ch orin.

4. As new articles of manufacture the coloringmatters containing halogen which can be obtained by treating a benzanthrone coloring-matter with a halo enlzing agent, which co oring-matters disso ve in sulfuric acidvyielding from violet to brown solutions, and

' from green to blue-vic in hot anilin yieldin' ich dissolve in alkaline let solutions, and w h drosulfite yielding blue tobluish-red vats W ich dye vegetable fiber substantively giving blue-violet to violet-blue shades.

5. As a new article of manufacture the col- OSCAR BALLY.

Witnesses J Arno. LLOYD, Jos. ILIJEUTE. 

